Monoazo dyestuffs and their metal complex compounds



United States Patent MONOAZO DYESTUFFS AND THEIR METAL COMPLEX COMPOUNDS Otto Senn, Arlesheim, near Basel, Hanspeter Uelilinger, Binningen, and Walter Wehrli, Riehen, near Basel, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland, a Swiss firm No Drawing. Application August 18, 1958 Serial No. 755,414

Claims priority, application Switzerland August 21, 1957 7 Claims. (Cl. 260-146) The present invention relates to a process for the production of monoazo dyestuffs and their metal complex compounds. The process consists in reacting 1 mol of a hydrazinobenzene, which contains in ortho-position to the hydrazino group a substituent capable of taking part in metal complex formation or capable of being converted so as to perform this function, with 1 mol of an orthodiketone and treating the so formed monoazo dyestuff in substance or on the fiber with a metal yielding agent, preferably one yielding chromium or cobalt.

The monoazo dyestuffs obtained according to the present invention correspond to the formula which is the enolized form of a a-ketohydrazone obtained by monocondensation of an ortho-diketone with the phenylhydrazine of the formula group or a sulfonic acid amide group, the latter of which may be substituted on the nitrogen atom.

The monoazo dyestuffs here disclosed are suitable for dyeing wool by the one-bath chrome process. The metal complex compounds are of value for the dyeing and printing of wool, silk, leather and polyamide fibers; those which have sufiiciently high solubility in organic solvents are of interest for dyeing manufactured fibers in the mass prior to spinning and for coloring plastics and lacquer media.

The dyeings and colorings obtained possess good fastness to light and wet treatments such as washing, milling, perspiration, potting and acids. Hydrazinobenzenes conforming to the present definition can be produced, for example, according to the particulars given in German Patent 258,0l7. Preference is given to the hydrazinobenzenes which contain an alkylsulfonyl group or a sulfonic acid amide group, the latter of which may be substituted on the nitrogen atom.

Other substitutents which enter into consideration for the above-defined hydrazinobenzenes are e.g. halogen atoms (chlorine), alkyl groups (methyl), the nitro group,

acylamino groups (acetylamino); these su bstituents; may

be present beside a sulfonic acid amide or alkyl sulfonyl group.

Of the sulfonic acid amide and the alkyl sulfonyl groups may be mentioned the sulfonic acid amide, sulfonie acid methylamide, sulfonic acid dimethylamide, sulfonic acid-(2-hydroxy)-ethylarnide, sulfonic acid di-(2'- hydroxyethyl)-amide, sulfonic acid (2'- or 3-hydroxy)- propylamide, sulfonic acid-(3-methoxy)-propylamide, sulfonic acid-(2'-ethoxy)-ethyl-amide, sulfonic acid phenylamide, sulfonic acid methylphenylamide or chlorophenylamide, sulfonic acid-(2'-carboxy)-phenylamide, sulfonic acid-N-methyl-N-phenylamide, sulfonic acid-N- (2'-hydroxy)-ethyl-N-phenylamide and the methyl sulfonyl group.

Examples of suitable ortho-diketones are l.2-benzoquinone, 9.IO-phenauthrenequinone, acenaphthenequinone and isatin, dibromoisatin, N-rnethylisatin and N-acetylisatin.

The reaction of the hydrazinobenzene with the orthodiketone is conducted preferably in an aqueous, strongly acid medium. In most instances the condensation product is precipitated; it is filtered oil, dissolved in excess alkali and reprecipitated in the form of the alkali metal salt, if desired after clarification of the solution by the addition of salt.

The monoazo dyestuffs are converted into their metal complex compounds preferably with chromium or cobalt compounds. The metallization is best carried out in an aqueous solution or an organic medium, for example formamide or ethyl glycol, or in the concentrated aqueous solution of an alkali metal salt of a low molecular aliphatic monocarboxylic acid. It is desirable to allow a quantity of metal-yielding agent containing at least one but less than two atoms of metal to act upon two molecules of the monoazo dyestuii.

The metal complex compounds so obtained are precipitated from aqueous medium by the addition of salt,

the organic metallizing solution being first run into water when the operation is carried out in non-aqueous medium. They are then filtered olf, washed if desired, and dried.

The metal-containing azo dyestulfs so formed are metal complex compounds in which essentially one metal atom is combined with two molecules of the monoazo compound. They can be described as 1:2 complexes in which one molecule proportion of the monoazo compound is combined with approximately 0.3 to 0.7 atom proportion of metal.

In the examples which follow the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 21.7 parts of 1-hydroxy-2-hydrazinobenzene-4-sulfonic acid methylamide are reacted in a strongly mineral acid solution with 18.2 parts of acenaphthenequinone finely suspended in water at -100 C. After about two hours condensation is complete. The precipitated dyestuff is filtered 0E, dissolved in water with excess sodium hydroxide, the solution filtered if necessary and the monoazo dyestuff precipitated by the addition of common salt. It is filtered off, dried and ground to give a dark powder which dyes wool by the one-bath chrome process in green shades of good fastness to light, washing, milling, plotting and acids.

A similar dyestuif is obtained when in place of 21.7 parts of 1-hydroxy-2-hydrazinobenzene-4-sulfonic acid methylamide, 27.5 parts of l-hydroxy-2-hydrazinobenzene-4-sulfonic acid-(3'-methoxy)-propylamide are employed for condensation.

parts of prewetted wool fabric are introduced at -30 into the solution of 2 parts of the monoazo dyestuif of anhydrous sodium sulfate, 6 parts of ammonium sulfate and l part of sodium bichromate in 6000 parts of a d PARAGRAPH 2' water. The bath is heated to the boil in the course of 30 on 130.; minutes and maintained at the boil for 90 minutes, the evaporated water being replaced from time to time. "The dyed wool is then removed from the bath, rinsed with water and dried.

31.8 parts of the monoazo dyestuff obtained according EXAMPLE 2 to Example 1, paragraph 1, are dissolved in 400 parts of formamide. The solution .is heated to 100-110 and chromuim coinplex compound 'contzimmg bound 30 parts of crystallized chromic ammonium sulfate are zp f i i i atom of g added to it in about 30 minutes. The mixture is mainy W0 f es 0 v e monoazo, yes u o Xamp e .tained at IUD-110 until formation ofthe chromium 'comlr FE I EXAMPLE 3 pics compound is complete, whereupon the chroming 0 I mass is diluted with 4 to 5 times its amount of water The cobaflt F P compound containing, bplmd 111 and the chromium complex compound salted out, filtered CQmpleX m with one atom 0f Cobalt, Substantially tWO ofi, dried and ground. The chromium containing dyestutf molecules Ihe 1110110320 dyfistufi 0f vExan'lple P is a dark'powder which dyes wool, silk, polyamidefibers ap and leather in green shades of good .fastness to light, Havmg thus'dlsclosedthe mventwnwhat e claim washing and milling. VI. A member selected from the group consisting of a EXAMPLE 3 .monoazo dyestufi which is vfree from sulfonic acid groups, I 7 is free'from carboxylic acid groups standing in a position parts of me monoazo dyestufi pfoducved 'f other thaniortho tothe'azo group and corresponds'to the mg to Example 1, paragraph 2, are dissolved with 30 [formula parts of an 18% cobalt acetate solution (equivalent to 4 1.77 parts of cobalt) in 400 parts of water at 80. By dropwise addition of sufficient 10% caustic soda the pH value of the solution is brought to 9.5. On completion zA--N==N-.-;Q' of metallization the cobaltiferous dyestufi is isolated and I dried, giving a dark powder which dyes wool, silk, leather and the chromium and cobalt complex compounds there and polyamide fibers in olive-green shades having good of, fas2tness to lifghg, waslgirlig and milling. d h b h i parts 0 t e co a t-containingazo yestu t us 0 x stands in urtho 0 -position to -NN and represents tamed are dissolved in 4000 parts of water at 40-50 35 a member Selected from the group consisting of a 100 parts of a previously Wetted out wool fabric are iiihydmxy and a carboxy group troduced into this dyebatii and 2 parts of 100% acetic Ho acid are dropped in. The bath is then brought to the boil in 30 minutes and boiled for minutes. The dyed wool is then taken out, rinsed with water and dried; the 40 -c dyeing shows very good fastness to light, washing .and milling. V I V represents the radical of -a member selected from the Further examples are set out in the .following table. group consisting of l-hydroxyacenaphthene, 9-hy- Table Shade of the Dyeings on W001 with Example .No. Hydrazlnobeuzene ortho-Dlketone the monoazo the ehrothe cobalt- -dyestufi :miuni-concontaining 212.0

Y chromedron taining'azo dyestufi the'fiber dyestufi .4 1-hydinxy-z-hydrazinobenzene-4-sulfonle acid isatiim r red orange-brown.

amt e. 5- Lhydroxy-z-hydrazinobenrene-t-sulfonie acidphenanthr'ene blue-riolet.- .blue-violeL. .bordeaux.

(3'-met,hoxyypropylamide. quiuone. 6 l-hydroxy-2-hydrazino-t-methylsulfouylbenzene. acg iaphm green... green olive. '7 1-carhoxy-2-hydrazinoben1min isatii i one orange orange yellow. 8 l-hydmxyfZ-hydrazinobenzene-4-sulfonic acidacenaphthene- 'green green olive.

morpbolide. qulnone. 9 1421x30;y-Z-hydrazinobenzenel-sulfonle acid 5.7-dibromoisatln--- red red brown-orange. 10 do .N-methyli inn (in ,Do, 11 d0 'N-acetyll atin 'fin 'do "D0. 12 -'acenaphthenegreen green ollvegreen.

qulnone.

Formulae of representative dyestuffs of the foregoing droxyphenanthrene,'2-hydroxyindole, 2-hydroxy-5,7ediexamples are as follows: 5 bromoindole, l methyle2=hydroxyindole and .l-acetylel- XA PL 1 hydroxy1ndole,'and

E M E .A represents a memberselected from the group-consist- PARAGRAPH 1 ing of a'furtherunsubstituted benzene radical and a further substituted 'benzene radical, 'the substituents I -bemg selected from the group consisting of methyl, chlorine, nitro, methylsulfonyl, sulfonic acid amide, :sulfonic acid lower Salkylamide, sulfonic acid lower hydroxyalkylamide, sulfonic acid lower alkoxyalkylamide, sulfonic acid 'phenylamide', sulfonic acid cycloso,Nn--on= 'ihexylaniideand sulfonic-acid morpholide;

2. A metal complex compound containing, bound in complex union with one atom of a metal selected from the group consisting of chromium and cobalt, substantially two molecules of a monoazo dyestuff free from sulfonic acid and carboxylic acid groups which corresponds to the formula SO2NH-R wherein R represents a member selected from the group consisting of hydrogen, methyl and methoxypropyl, and

represents the radical of 1hydroxyacenaphthene.

3. The chromium complex compound containing, bound in complex union with one atom of chromium, substantially two molecules of the monoazo dyestufi of the formula OH HO-C SOz-NH-CH;

4. The cobalt complex compound containing, bound in complex union with one atom of cobalt, substantially two molecules of the monoazo dyestufi of the formula 5. A metal complex compound containing, bound in 50 complex union with one atom of a metal selected from the group consisting of chromium and cobalt, substantially two molecules of a monoazo dyestufi free from 'sulfonic acid and carboxylic acid groups which corresponds to the formula S 02-NH2 7. The cobalt complex compound containing, bound in complex union with one atom of cobalt, substantially two molecules of the monoazo dyestufi of the formula 111 Br N 03 HOC/ SOz-NH:

References Cited in the file of this patent UNITED STATES PATENTS Pfitzner et a1. Oct. 14, 1958 OTHER REFERENCES Zincke: Ber. Deut. Chem., 16, pp. 1563-4564 (1883).

Zincke et al.: Ber. Deut. Chem, 17, p. 3032 (1884).

Taylor et al.: Sidgwicks Organic Chemistry of Nitrogen, 1949, pp. 439-440. 

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF A MONOAZO DYESTUFF WHICH IS FREE FROM SULFONIC ACID GROUPS, IS FREE FROM CARBOXYLIC ACID GROUPS STANDING IN A POSITION OTHER THAN ORTHO TO THE AZO GROUP AND CORRESPONDS TO THE FORMULA 